Reaktion #67471

Reaktionsgleichung

2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol

Cyanomethylenetributylphosphorane

Tin(II) chloride dihydrate

→

3-bromo-4-(3-methyloxetan-3-yl)aniline

Ausbeute 32.0%

Lösungsmittel

benzene

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe mixture was evaporated to dryness
2. 2
   workup.DISSOLUTIONre-dissolved in 4 mL of EtOH
3. 3
   Temperaturthe resulting solution was heated at 70° C. for 1 hour
4. 4
   TemperaturThe mixture was cooled to room temperature
5. 5
   Sonstigequenched with a saturated aqueous solution of sodium bicarbonate
6. 6
   ExtraktionThe mixture was then extracted three times with ethyl acetate
7. 7
   SonstigeThe combined ethyl acetate extracts were evaporated to dryness
8. 8
   Sonstigepurified by preparative LC/MS

Vorschrift

2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol (0.145 g, 0.500 mmol) was dissolved in 2.5 mL of anhydrous benzene. Cyanomethylenetributylphosphorane (CMBP) (0.181 g, 0.750 mmol) was then added and the solution was allowed to stir at room temperature for 72 hours. The mixture was evaporated to dryness and then re-dissolved in 4 mL of EtOH. Tin(II) chloride dihydrate (0.564 g, 2.50 mmol) was then added and the resulting solution was heated at 70° C. for 1 hour. The mixture was cooled to room temperature and then quenched with a saturated aqueous solution of sodium bicarbonate. The mixture was then extracted three times with ethyl acetate. The combined ethyl acetate extracts were evaporated to dryness and purified by preparative LC/MS to yield 3-bromo-4-(3-methyloxetan-3-yl)aniline as a pale yellow oil (0.032 g, 32%) NMR (400 MHz, CD3CN) δ 7.13 (dd, J=0.7, 1.8 Hz, 1H), 6.94-6.88 (m, 2H), 6.75 (br s, 2H), 4.98 (d, J=5.6 Hz, 2H), 4.51 (d, J=6.1 Hz, 2H), 1.74 (s, 3H). ESI-MS m/z calc. 241.0, found; 242.1 (M+1)+ Retention time 0.53 minutes.

Quelle